Coloring of materials made with or containing cellulose derivatives



Patented Aug. 4, 1936 UNITED STATES PATENT OFFICE COLORING OF MATERIALS MADE WITH OR CONTAINING CELLULOSE DERIVATIVES No Drawing. Application June 22, 1928, Serial No. 287,643. In Great Britain July 19, 1927 made of or containing cellulose ethers, such for example as methyl, ethyl, or benzyl cellulose; or the corresponding condensation products of cellulose and glycols or other polyhydric alcohols, all of-which cellulose derivatives are hereinafter referred to as organic substitution derivatives of cellulose.

According to the present invention materials made of or containing cellulose acetate or other 20 of the aforesaid organic substitution derivatives of cellulose are dyed or otherwise colored with I azo coloring matters in the production of which an aminonaphthol is employed as a component.

The term component is used to include the cou- 25 pling component and the component which is diazotized and coupled therewith. The aminonaphthols employed may or may not be substituted in the nucleus.

The coloring matters for use according to the 30 present invention may be of any desired series.

Thus for example monoazo dyestufis may be obtained by coupling a suitable diazo. body of the benzene or naphthalene series with an aminonaphthol in acid or alkaline solution or by di- 35 a'zotizing an aminonaphthol and coupling with an end component for example of the benzene or naphthalene series or with the same or a different aminonaphthol (in acid or alkaline solution) and such dyestuffs may if desired be sub- 40 sequently diazotized on the fibre and developed suitable end component for example of the ben-' 50 zene or naphthalene series. Primary vdisazo dyestuffs may be obtained for use according to the.

present invention by coupling one molecular pro portion of a suitable diazotized amine with an aminonaphthol in acid solution and then render- 55 ing the solution alkaline and coupling with a ,as described in prior U. Patents Nos. 1,618,413

further molecular proportion 'of the same or, different diazotized amine or if desired the first coupling may be in acid and the second in alkaline solution. .Secondary disazo dyestuffs may be obtained for example by diazotizing a suitable aminoazo compound such for example as benzene-azo-a-naphthyl-amine or aminoazobenzene or their nuclear substitution derivatives or by diazotizing one amino group of a diaminoazo compound, e. g., p.p'-diaminoazobenzeneor 4-amino- 10 benzene-1-azo-4-aminonaphthalene and coupling the resulting diazo compound with an aminonaphthol or by diazotizing a suitable amine, coupling with an aminonaphthol and diazotizing the resulting compoundv and coupling with the same or different aminonaphthol or other suitablecoupling component. The disazo dyestufis when containing diazotizable amino group may be diazotized on the material and developed.

The above examples of the methods of forming the dyestuffs and of the difierent series of dyestufis which may be used according to the present invention are intended to be illustrative and not to limit the invention.

Where nitroamines, such as p-nitraniline, or 5 monoacidyl diamines such as p-aminoacetanilide or p-aminophenyloxamic acid have been used in the preparation of the dyestuffs, the nitro or acidyl amino groups may be reduced or hydrolyzed as the case may be, the resulting compounds being particularly useful for diazotization and development on the fibre. I

Many of the dyestuffs and particularly those containing only one azo grouping attached to the naphthalene nucleus of the aminonaphthol may be developed on the fibre with a suitable diazo body.

We have found that the dyestufis containing the azo group linked to the naphthalene nucleus in a position ortho or peri to an auxochrome 40 group and especially those obtained from 1- amino-8-naphthol and its nuclear substituted derivatives by coupling in the 'ortho position to the auxochrome groups give particularly useful colorings.

The dyestuffs, if soluble or fairly soluble in neutral, slightly alkaline or slightly acid solution, may be applied directly from such an aqueous medium with or without the addition of a dispersing agent, or if insoluble or only slightly soluble in water they may be applied from dispersions in water obtained by any of the methods known in the colloid arts, for example by pretreatment of the dyestuffs with s'olubill zing agents 1,618,414, 1,690,481 and 1,694,413 and U. S. applications S. Nos. 152,517 filed December 3, 1926, 134,138 filed September '7, 1926-and 176,289 filed March 17, 1927.

The following are a number of examples of the dyestuffs which 'may be applied according to the present invention:-

Aniline-al-amino-S-naphthol Red (coupled alkaline) p-Xylidine 2-amino-3-naphthol Red p-N1traniline l-ammo-8-naphthol XPiZaniune Blue lk. Dianisidine -ll-amino-8-naphthol (2 mols.) Bluish-grey DianisidinfELll-amino-8-naphthol (2 mols.) Dark brown p-Aminobenzeneazo-lamino- S-naphthol (coupled alkaline) Puce The process of theinvention may be applied to the dyeing or otherwise coloring of mixed goods comprising for example, in addition to cellulose acetate or other organic substitution derivative of cellulose, silk, wool or cotton or other cellulosic fibre, natural or artificial, in solid or differential shades according to the affinity of the dyestuffs for the fibres used inas sociation.

The following examples illustrate the invention, it being understood that they are not intended to limit it.

Example 1.--To dye 10 kilograms of cellulose acetate fabric a red shade.

100 grams of the dyestufi benzene-azo-l-amino- B-naphthol are I reduced to a fine powder and stirred into 600 grams of 50% sodium sulphoricinoleate. The resulting mixture is heated to 90- 95 C. and stirred till as homogeneous as possible.

It is now diluted with litres of boiling soft water, stirred well, and passed through a filter cloth into a dyebath containing 300 litres soft water, in which have been dissolved 50 grams Marseilles soap. The fabric is entered, and dyeing carried out by raising the temperature to 75-80" C. during hour, maintaining at this temperature till exhausted. The fabric, which is now dyed a full red shade, is rinsed, and dried or otherwise treated as desired.

Example 2.To dye a black shade on kilos of cellulose acetate yarn iri'hank form.

200 grams of the dyestuff p-aminobenzeneazol-amino-B-naphthol (prepared by coupling di- .azotized p-nitraniline with I-amino-S-naphthol Percent on wt.

. of goods Betahydroxynaphthoic acid 3 Caustic soda 0.7

Glue 5 .1 30:1 bath is prepared with the above at 35 C. and 5% acetic acid added immediately before entering the goods. Coupling commences immediately and the bath is slowly raised to 60 C. and maintained at this temperature till complete. The goods are now lightly soaped, and dried or otherwise treated as desired.

Example 3'.--To dye 10 kilos of cellulose acetate fabric a dark brown shade.

' 100 grams of the dyestufi prepared from (1 molecule) tetrazotized dianisidine and (2 molecules) 1 amino-S-naphthol by coupling in alkaline solution, are applied to the fibre by the method detailed in Example 1, or. by other suitable method, and the goods afterrinsing, entered into a bath of a /4% solution of p-nitrobenzenediazonium acetate at normal temperature, worked for hr., lifted, rinsed, and dried or otherwise treated as desired.

Instead of the cellulose acetate materials treated in the above examples, materials made of "1. containing other organic substitution derivatives of cellulose, for example, cellulose formate, cellulose propionate, methyl cellulose, ethyl cellulose, immunized cotton etc., may be similarly colored and instead of dyestuffs derived from 1.8-aminonaphthol dyes derived from other amincnaphthols may be employed.

The term dyeing in the appended claims is to be understood to include printing, stencilling or otherwise coloring.

.What we claim and desire to secure by Letters Patent is:--

1. Process of dyeing materials comprising organic substitution derivatives of cellulose characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which an aminonaphthol is employed as a component.

2. Process of dyeing materials comprising organic substitution derivatives of cellulose characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which an aminonaphthol is employed as a component and which contains azo group in the ortho position to an auxochrome group of the naphthalene nucleus.

3. Process of dyeing materials comprising organic substitution derivatives of cellulose characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which a 1.8 aminonaphthol is employed as a component.

4. Process of dyeing materials comprising cellulose acetate characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which an aminonaphthol is employed as a component.

5. Processof dyeing materials comprising cellulose acetate characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which an aminonaphthol is employed as a component and which contains the azo group in the ortho position to an auxochrome group of the naphthalene nucleus.

6. Process of dyeing materials comprising cellulose acetate characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which a.1.8 aminonaphthol is employed as a component.

7. Process of dyeing materials comprising cellulose acetate characterized in that said materials arecolored by means of an unsulfonated azo dyein the production of which an aminonaphthol is employed as .a component, diazotizing the dyestuif on the material and developing.

8. Process of dveing materials comprising cellulose acetate characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which an aminonaphthol is employed as a component and which contains the azo group in the ortho position to an auxochrome group of the naphthalene nucleus, diazotizing the dyestufi on the material and developing. v

9. Process of dyeing materials comprising cellulose acetate characterized in that said materials are colored by means of an unsulfonated azo dye in the production of which a. 1.8 aminonaphthol is employed as a component, diazotizing the dyestuff on the material and developing. 5

GEORGE HOLLAND ELLIS. HENRY CHARLES OLPIN. ERNEST WILLIAM KIRK. 

